JP2008164730A - Hologram recording layer forming composition, hologram recording material and hologram optical recording medium using the same - Google Patents

Abstract

〔Ｒ²は、炭素数２〜２０のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、ベンゾイル基、炭素数２〜１０のアルコキシカルボニル基、フェノキシカルボニル基、炭素数１〜２０のヘテロアリール基、炭素数１〜２０のヘテロアリーロイル基、又は炭素数１〜２０のアミノカルボニル基。Ｘ，Ｙは任意の置換基。〕
【選択図】図１Disclosed is a hologram optical recording medium that is excellent in solubility in a solvent and excellent in recording sensitivity when performing hologram recording using a laser beam in a blue-violet to visible light region.
A composition for forming a hologram recording layer capable of forming a photoimage, which contains a polymerizable photoactive compound (a) and is used for a hologram optical recording medium. A compound having the structure of the following general formula (I), including a photopolymerization initiator (b) having an absorption maximum in a wavelength region of 340 to 700 nm and a solubility in toluene of 1 (g / 100 g) or more. .

[R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group, A heteroaryl group having 1 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, or an aminocarbonyl group having 1 to 20 carbon atoms. X and Y are arbitrary substituents. ]
[Selection] Figure 1

Description

  The present invention relates to a composition for forming a hologram recording layer, and a hologram recording material and a hologram optical recording medium using the composition.

  2. Description of the Related Art In recent years, a hologram type optical recording medium that records information as a hologram by changing the refractive index of the recording layer according to the light intensity distribution due to the interference of light toward further increase in capacity and density of the optical recording medium. Has been developed.

  General principles regarding hologram production are described in several documents and technical books (see Non-Patent Document 1). According to these, one of the two light fluxes of coherent laser light is irradiated onto the recording object, and the photosensitive hologram recording material is placed at a position where the light can be received. The hologram recording material is directly irradiated with the other coherent light in addition to the light from the object without hitting the object. Light from the object is referred to as object light, and light directly applied to the recording material is referred to as reference light, and interference fringes between the reference light and object light are recorded as image information. Next, when the processed recording material is irradiated with the same light (reproduction light) as the reference light, it is diffracted by the hologram so as to reproduce the wavefront of the reflected light that first reaches the recording material from the object during recording. As a result, the same object image as the real image of the object can be observed three-dimensionally. A hologram formed by making the reference light and the object light incident on the hologram recording material from the same direction is called a transmission hologram, and a hologram formed by making the reference light and the object light incident from the opposite side is called a reflection hologram. A hologram whose volume is sufficiently thick with respect to the interference fringe interval (usually a thickness of 5 times or more of the interference fringe interval or about 1 μm or more) is called a volume hologram, and recording can be performed in the film thickness direction. The larger the film thickness, the higher the density recording is possible.

  As an example of a known volume phase hologram recording material, there is a write-once type that does not require wet treatment or bleaching treatment, and its composition is generally a resin matrix in which a photoactive compound is compatible. For example, there is a photopolymer type recording material in which a resin matrix is combined with a monomer capable of radical polymerization or cationic polymerization (see Patent Documents 1 to 4).

  At the time of recording information, when object light and reference light are irradiated, interference fringes composed of a bright part and a dark part are formed on the recording layer. For example, when the photoactive compound is a radical polymerizable compound, in the bright part, the photopolymerization initiator absorbs light and changes to a radical active species. This radical active species undergoes an addition reaction with a neighboring radical polymerizable compound, and the addition product is changed to a radical active species. Further, the addition product that has become the radical active species undergoes an addition reaction with a neighboring radical polymerizable compound. By repeating this series of photopolymerization reactions, a bright polymer is generated in the recording layer. On the other hand, the radical polymerizable compound has a concentration gradient in the light portion polymerization reaction, and the radical polymerizable compound in the dark portion of the recording layer diffuses and moves to the bright portion, and conversely, other components in the light portion. Diffuses to the dark. Thereby, the bright part and dark part of an interference fringe are comprised by a different compound, and come to have a different refractive index. As a result, the hologram optical recording medium holds this refractive index difference as information. Since the diffraction efficiency increases as the difference in refractive index increases, the use of a compound having an aromatic ring, a hetero ring, chlorine, bromine or the like in either the resin matrix or the monomer in order to provide a difference in refractive index. Has been made.

  Photopolymer recording materials are generally composed of a resin matrix, a photoactive compound, and a photopolymerization initiator, and are practical and promising methods that can achieve both high diffraction efficiency and dry processing. Therefore, there is a demand for high sensitivity, sufficient diffraction efficiency, high S / N ratio, high multiplicity, and excellent recording signal stability and reliability. In order to achieve these, various studies have been made on the composition of the recording composition and the production method of the medium.

By the way, at the time of recording on the hologram optical recording medium, a photopolymerization initiator for performing interference exposure is indispensable, but it is desirable to add at a certain high concentration (for example, 5% by weight) in order to improve sensitivity. When a blue-violet to visible light region laser is used for hologram recording, it is preferable to use a photopolymerization initiator having absorption in the wavelength region, that is, a range of 340 to 700 nm. As such a photopolymerization initiator, it is known to use an oxime ester photopolymerization initiator having a specific structure. However, since these are generally poorly soluble in a solvent, a necessary amount can be dissolved. In some cases, this is not possible, and as a result, the sensitivity is lowered (Patent Document 5).
Junpei Tsubouchi "Holographic Display" Chapter 2, Industrial Books Japanese Patent No. 3737306 JP 2005-43862 A JP-T-2005-502918 JP 2004-158117 A WO02 / 100903

  The present invention has been made in view of the above problems, and its purpose is excellent in solubility in a solvent and excellent in recording sensitivity when performing hologram recording using a laser beam in a blue-violet to visible light region. The object is to provide a hologram optical recording medium.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are compounds having a structure of the following general formula (I) in a photoimageable system containing a polymerizable photoactive compound (a). Yes, by using a photopolymerization initiator (b) having an absorption maximum in the wavelength range of 340 to 700 nm and a solubility in toluene of 1 (g / 100 g) or more, the solubility in a solvent is excellent. Therefore, it has been found that the sensitivity of the composition for forming a hologram recording layer or a hologram optical recording medium using the composition can be improved, and the present invention has been completed.
That is, the gist of the present invention is as follows.

〔式中、Ｒ²は、それぞれ置換基を有していても良い、炭素数２〜２０のアルカノイル基、炭素数３〜２５のアルケノイル基、炭素数３〜８のシクロアルカノイル基、ベンゾイル基、炭素数２〜１０のアルコキシカルボニル基、フェノキシカルボニル基、炭素数１〜２０のヘテロアリール基、炭素数１〜２０のヘテロアリーロイル基、又は炭素数１〜２０のアミノカルボニル基を示す。
Ｘ，Ｙはそれぞれ独立して任意の置換基を示す。〕 [1] A composition for forming a holographic recording layer capable of forming a photoimage containing a polymerizable photoactive compound (a) used for a holographic optical recording medium, and having a structure represented by the following general formula (I) And a photopolymerization initiator (b) having an absorption maximum in a wavelength region of 340 to 700 nm and a solubility in toluene of 1 (g / 100 g) or more. Composition.

[In the formula, each R ² optionally has a substituent, an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a benzoyl group, An alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group, a heteroaryl group having 1 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, or an aminocarbonyl group having 1 to 20 carbon atoms is shown.
X and Y each independently represent an arbitrary substituent. ]

〔式中、Ｒ¹は、水素原子、置換基を有していても良い炭素数１〜２０のアルキル基、置換基を有していても良い炭素数１〜１２のアミノアルキル基、置換基を有していても良い炭素数２〜２０のアルケニル基、又は下記一般式（IIａ）で表される基を示す。

（式中、Ｒ^2"、Ｒ^3'、Ｒ^4'、Ｒ^5'、Ｒ^6'及びＲ^7'は、それぞれ一般式（II）におけるものとは独立して一般式（II）におけるＲ^2'、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷と同義である。また、式中の＊は、＊の部分で一般式（II）における炭素原子に結合することを意味する。）
Ｒ^2'は、それぞれ置換基を有していても良い、炭素数２〜１２のアルカノイル基、炭素数４〜６のアルケノイル基、ベンゾイル基、炭素数２〜６のアルコキシカルボニル基、フェノキシカルボニル基を示す。
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、フェノキシカルボニル基、或いは、−ＯＲ⁸、−ＳＲ⁹、−ＳＯＲ⁹、−ＳＯ₂Ｒ⁹若しくは−ＮＲ¹⁰Ｒ¹¹を示し、かつ、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷の少なくとも一つは、−ＯＲ⁸、−ＳＲ⁹、又は−ＮＲ¹⁰Ｒ¹¹を示す。
ただし、Ｒ⁸は、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜８のアルカノイル基、炭素数３〜１２のアルケニル基、炭素数３〜６のアルケノイル基、炭素数３〜１５のシクロアルキル基、フェニル基、−（ＣＨ₂ＣＨ₂Ｏ）_nＨ（ｎは１〜２０の整数）、又は炭素数３〜２０のアルキルシリル基を示す。
Ｒ⁹は、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケニル基、炭素数３〜１５のシクロアルキル基、又はフェニル基を示す。
Ｒ¹⁰及びＲ¹¹は、互いに独立して、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜１２のアルカノイル基、炭素数３〜６のアルケノイル基、炭素数３〜５のアルケニル基、炭素数５〜１２のシクロアルキル基、フェニル基、ベンゾイル基、又は、ビフェニル基を示す。フェニル基、ベンゾイル基、ビフェニル基は、置換されていても良い炭素数２〜８のアルキレン基を介して結合していても良い。
また、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに結合し環構造を形成してもよい。〕 [2] The composition for forming a hologram recording layer according to [1], wherein the photopolymerization initiator (b) is a compound represented by the following general formula (II).

[Wherein, R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aminoalkyl group having 1 to 12 carbon atoms, or a substituent. Or an alkenyl group having 2 to 20 carbon atoms, or a group represented by the following general formula (IIa).

Wherein R ^{2 ″} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′} and R ^{7 ′} are each independently R ² in the general formula (II) independently of that in the general formula (II). ^′ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7, and * in the formula means bonding to a carbon atom in the general formula (II) at the portion *.
R ^{2 ′} each may have a substituent, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group. Indicates.
R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, carbon, which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 Represents an alkoxycarbonyl group, a phenoxycarbonyl group, or —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ^6. And at least one of R ⁷ represents —OR ⁸ , —SR ⁹ , or —NR ¹⁰ R ¹¹ .
However, R ⁸ is a hydrogen atom, or, respectively may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, carbon An alkenoyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a phenyl group, — (CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20), or alkylsilyl having 3 to 20 carbon atoms Indicates a group.
R ⁹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or phenyl. Indicates a group.
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or 3 to 3 carbon atoms, each optionally having a substituent. An alkenoyl group having 6 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzoyl group, or a biphenyl group; The phenyl group, benzoyl group, and biphenyl group may be bonded via an optionally substituted alkylene group having 2 to 8 carbon atoms.
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure. ]

〔式中、Ｒ¹及びＲ^2'は、それぞれ一般式（II）におけるＲ¹及びＲ^2'と同義である。
Ｒ^3"、Ｒ^6"及びＲ^7"は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、又はフェノキシカルボニル基を示す。
Ｒ¹²、Ｒ¹³、Ｒ¹⁴及びＲ¹⁵は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜２０のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、又はフェノキシカルボニル基、或いはアミド基又はニトロ基を示す。〕 [3] The hologram recording layer forming composition as described in [2], wherein the photopolymerization initiator (b) is a compound represented by the following general formula (III).

Wherein, R ¹ and R ^{2 'are} R ¹ and R ² in the general formula ^(II)' is synonymous with.
R ^{3 ″} , R ^{6 ″} and R ^{7 ″} each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 3 to 3 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 12 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A group or a phenoxycarbonyl group;
R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 2 to 2 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 20 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A group, a phenoxycarbonyl group, an amide group or a nitro group; ]

〔式中、Ｒ¹及びＲ^2'は、それぞれ一般式（II）のおけるＲ¹及びＲ^2'と同義である。
Ｒ^3"'、Ｒ^6"'及びＲ^7"'は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、又はフェノキシカルボニル基を示す。
Ｒ^12'、Ｒ^13'、Ｒ^14'及びＲ^15'は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜２０のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、又はフェノキシカルボニル基、或いはアミド基又はニトロ基を示す。
Ｒ¹⁶は、ヒドロキシル基、チオール基、ニトロ基、シアノ基、或いは、それぞれ置換基を有していても良い、炭素数３〜１８のシクロアルケニル基、炭素数１〜１８のアルキルチオ基、炭素数６〜１８のアリール基、炭素数２〜１８のアルケニルオキシ基、炭素数２〜１８のアルケニルチオ基、アシル基、カルボキシル基、アシルオキシ基、アミノ基、アシルアミノ基、カーバメート基、カルバモイル基、カルボン酸エステル基、スルファモイル基、スルホン酸エステル基、オキサゾリル基、ベンゾキサゾリル基、チアゾリル基、ベンゾチアゾリル基、モルホリノ基、ピロリジニル基、テトラヒドロチオフェンジオキサイド基、又はトリアルキルシリル基を示す。〕 [4] The composition for forming a hologram recording layer according to [2], wherein the photopolymerization initiator (b) is a compound represented by the following general formula (IV).

[Wherein, R ¹ and R ^{2 ′} have the same meanings as R ¹ and R ^{2 ′ in} formula (II), respectively.
R ^{3 ″ ′} , R ^{6 ″ ′} and R ^{7 ″ ′} are independently of each other a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 An alkoxycarbonyl group or a phenoxycarbonyl group.
R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C20 alkanoyl group, C2-C2 12 alkoxycarbonyl groups, phenoxycarbonyl groups, amide groups or nitro groups are shown.
R ¹⁶ is a hydroxyl group, a thiol group, a nitro group, a cyano group, or a cycloalkenyl group having 3 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, or a carbon number, each optionally having a substituent. 6-18 aryl group, C2-C18 alkenyloxy group, C2-C18 alkenylthio group, acyl group, carboxyl group, acyloxy group, amino group, acylamino group, carbamate group, carbamoyl group, carboxylic acid An ester group, a sulfamoyl group, a sulfonic acid ester group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a tetrahydrothiophene dioxide group, or a trialkylsilyl group. ]

[5] The composition for forming a hologram recording layer according to any one of [1] to [4], further comprising a resin matrix (c).

[6] The composition for forming a hologram recording layer according to any one of [1] to [5], wherein the photoactive compound (a) is a radical polymerizable monomer.

[7] A hologram recording material comprising the composition for forming a hologram recording layer according to any one of [1] to [6].

[8] A hologram optical recording medium comprising a layer containing the hologram recording material according to [7].

  According to the present invention, a hologram optical recording medium having excellent solubility in a solvent and excellent recording sensitivity when performing hologram recording using a blue-violet laser beam can be obtained.

  Hereinafter, the best mode (embodiment) for carrying out the present invention will be described. The following description is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist. . Further, the drawings used are used for explaining the embodiments of the present invention, and do not represent actual sizes.

[I. Hologram recording layer forming composition]
The composition for forming a hologram recording layer of the present invention is a composition for forming a hologram recording layer capable of forming a photoimage containing a polymerizable photoactive compound (a) used for a hologram optical recording medium, A compound having a specific structure, comprising a photopolymerization initiator (b) having an absorption maximum in a wavelength range of 340 to 700 nm and a solubility in toluene of 1 (g / 100 g) or more. .

<Photoactive compound having polymerizability (a)>
The kind of the photoactive compound (a) having a polymerizable property used in the composition for forming a hologram recording layer of the present invention is not particularly limited and can be appropriately selected from known compounds. A monomer having polymerizability is used. Examples of the polymerizable monomer include a cation polymerizable monomer, an anion polymerizable monomer, and a radical polymerizable monomer.

(Cationically polymerizable monomer)
Examples of the cationic polymerizable monomer include compounds having an oxirane ring, styrene and derivatives thereof, vinyl naphthalene and derivatives thereof, vinyl ethers, N-vinyl compounds, and compounds having an oxetane ring. Among them, it is preferable to use a compound having at least an oxetane ring, and it is more preferable to use a compound having an oxirane ring together with a compound having an oxetane ring.

  Examples of the compound having an oxirane ring include a prepolymer containing two or more oxirane rings in one molecule. Examples of such prepolymers include cycloaliphatic polyepoxies, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, poly (aromatic polyols). Examples thereof include glycidyl ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. Any of these prepolymers may be used alone, or two or more thereof may be used in any combination and ratio.

  Examples of styrene and its derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, divinyl Examples include benzene.

  Examples of vinyl naphthalene and its derivatives include 1-vinyl naphthalene, α-methyl-1-vinyl naphthalene, β-methyl-1-vinyl naphthalene, 4-methyl-1-vinyl naphthalene, 4-methoxy-1-vinyl naphthalene. Etc.

  Examples of vinyl ethers include isobutyl ether, ethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-methoxyphenyl vinyl ether, and the like.

  Examples of the N-vinyl compound include N-vinyl carbazole, N-vinyl pyrrolidone, N-vinyl indole, N-vinyl pyrrole, N-vinyl phenothiazine and the like.

  Examples of the compound having an oxetane ring include various known oxetane compounds described in JP-A Nos. 2001-220526 and 2001-310937.

  Any one of the above-exemplified cationic polymerizable monomers may be used alone, or two or more may be used in any combination and ratio.

(Anionic polymerizable monomer)
Examples of anionic polymerizable monomers include hydrocarbon monomers and polar monomers.

  Examples of the hydrocarbon monomer include styrene, α-methylstyrene, butadiene, isoprene, vinyl pyridine, vinyl anthracene, and derivatives thereof.

  Examples of polar monomers include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate; acrylic acid esters such as methyl acrylate and ethyl acrylate; methyl vinyl ketone, isopropyl vinyl ketone, and cyclohexyl vinyl ketone. , Vinyl ketones such as phenyl vinyl ketone; isopropenyl ketones such as methyl isopropenyl ketone and phenyl isopropenyl ketone; other polarities such as acrylonitrile, acrylamide, nitroethylene, methylenemalonate, cyanoacrylate, vinylidene cyanide Monomer; and the like.

  Any one of the above-exemplified anionic polymerizable monomers may be used alone, or two or more thereof may be used in any combination and ratio.

(Radically polymerizable monomer)
The radical polymerizable monomer is a compound having one or more ethylenically unsaturated double bonds in one molecule, and examples thereof include (meth) acrylic acid esters, (meth) acrylamides, vinyl esters, Examples thereof include styrenes.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, (n- or i-) propyl (meth) acrylate, (n-, i-, sec- or t-). Butyl (meth) acrylate, amyl (meth) acrylate, adamantyl (meth) acrylate, chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypentyl (meth) Acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenze (Meth) acrylate, hydroxybenzyl (meth) acrylate, hydroxyphenethyl (meth) acrylate, dihydroxyphenethyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate, hydroxyphenyl (meth ) Acrylate, chlorophenyl (meth) acrylate, sulfamoylphenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2- (hydroxyphenylcarbonyloxy) ethyl (meth) acrylate, phenol EO modified (meth) acrylate, parac Milphenol EO modified (meth) acrylate, nonylphenol EO modified (meth) acrylate, N-acryloyloxyethylhexahydrofur Luimide, bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate, dibromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl acrylate, tricyclode Examples include candimethylol di (meth) acrylate and bisphenoxyethanol full orange (meth) acrylate. (“EO” represents “ethylene oxide”.)

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-benzyl. (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N- (hydroxyphenyl) (meth) acrylamide, N- (sulfamoylphenyl) ( (Meth) acrylamide, N- (phenylsulfonyl) (meth) acrylamide, N- (tolylsulfonyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N- Hydroxyethyl-N- Chill (meth) acrylamide.

  Examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl benzoate, vinyl t-butyl benzoate, vinyl chlorobenzoate, vinyl 4-ethoxybenzoate, vinyl 4-ethylbenzoate, 4- Examples include vinyl methylbenzoate, vinyl 3-methylbenzoate, vinyl 2-methylbenzoate, vinyl 4-phenylbenzoate, and vinyl pivalate.

  Examples of styrenes include styrene, p-acetylstyrene, p-benzoylstyrene, 2-butoxymethylstyrene, 4-butylstyrene, 4-sec-butylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3 -Chlorostyrene, 4-chlorostyrene, dichlorostyrene, 2,4-diisopropylstyrene, dimethylstyrene, p-ethoxystyrene, 2-ethylstyrene, 2-methoxystyrene, 4-methoxystyrene, 2-methylstyrene, 3-methyl Examples thereof include styrene, 4-methylstyrene, p-methylstyrene, p-phenoxystyrene, p-phenylstyrene, and the like.

  Any one of the radically polymerizable monomers exemplified above may be used alone, or two or more thereof may be used in any combination and ratio.

  Any of the above-exemplified cationic polymerizable monomers, anionic polymerizable monomers, and radical polymerizable monomers may be used, or two or more of them may be used in combination. However, since it is difficult to inhibit the reaction that forms the resin matrix, it is preferable to use a radical polymerizable monomer as the photoactive compound.

<Photopolymerization initiator (b)>
The photopolymerization initiator (b) used in the composition for forming a hologram recording layer of the present invention generates an active species such as a radical, an acid, or a base when irradiated with an actinic ray. It is a compound that leads to polymerization of the active compound.
The composition for forming a hologram recording layer of the present invention has a specific structure, has an absorption maximum in a wavelength range of 340 to 700 nm, and has a solubility in toluene of 1 (g / 100 g) or more. It is essential to contain an agent.

(Wavelength range of absorption maximum of photopolymerization initiator)
The absorption wavelength region of the photopolymerization initiator (b) constituting the composition for forming a hologram recording layer of the present invention has an absorption maximum at 340 nm or more, preferably 350 nm or more, and 700 nm or less, preferably 650 nm or less. is there. For example, when the light source is a blue laser, it preferably has an absorption maximum at 350 to 430 nm, and when the light source is a green laser, it preferably has an absorption maximum at 500 to 550 nm. When the absorption wavelength region is different from the above range, the irradiated light energy cannot be used efficiently for the photopolymerization reaction, resulting in low sensitivity.

The absorption maximum of the photopolymerization initiator can be easily measured, for example, by measuring a solution obtained by dissolving the photopolymerization initiator in a tetrahydrofuran solvent so as to have a concentration of about 10 ⁻⁵ mol with a normal ultraviolet or visible light absorption spectrum meter. Is required.

(Solubility of photopolymerization initiator)
The solubility of the photopolymerization initiator (b) constituting the hologram recording layer forming composition of the present invention is 1 (g / 100 g) or more in toluene under the conditions of 25 ° C. and 1 atm. (G / 100g) or more is preferable. Among the oxime ester initiators that are essential components of the photopolymerization initiator described later, those having the above-mentioned absorption maximum are generally solvents such as toluene, THF (tetrahydrofuran), MEK (methyl ethyl ketone), and (meth) acrylic acid. In many cases, the photopolymerization initiator (b) used in the present invention is poor in a solvent such as toluene, THF, MEK, or a photoactive compound such as (meth) acrylic acid ester. Since it has excellent solubility, it can be used in a composition for forming a hologram recording layer.

(Structure of essential components of photopolymerization initiator)
The photopolymerization initiator (b) constituting the composition for forming a hologram recording layer of the present invention is characterized by being represented by the following general formula (I).

[In the formula, each R ² optionally has a substituent, an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a benzoyl group, An alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group, a heteroaryl group having 1 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, or an aminocarbonyl group having 1 to 20 carbon atoms is shown.
X and Y each independently represent an arbitrary substituent. ]

  Here, the alkanoyl group includes an alkoxycarbonylalkanoyl group, a phenoxycarbonylalkanoyl group, and a heteroaryloxycarbonylalkanoyl group in addition to those substituted by the substituent described in [b-7].

  Among the compounds having the structure of general formula (I), preferred compounds are those represented by general formula (II).

〔式中、Ｒ^2"、Ｒ^3'、Ｒ^4'、Ｒ^5'、Ｒ^6'及びＲ^7'は、それぞれ一般式（II）におけるものとは独立して一般式（II）におけるＲ^2'、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷と同義である。また、式中の＊は、＊の部分で一般式（II）における炭素原子に結合することを意味する。）
Ｒ^2'は、それぞれ置換基を有していても良い、炭素数２〜１２のアルカノイル基、炭素数４〜６のアルケノイル基、ベンゾイル基、炭素数２〜６のアルコキシカルボニル基、フェノキシカルボニル基を示す。
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに独立して、水素原子、ハロゲン原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケノイル基、炭素数１〜１２のアルコキシ基、炭素数５〜８のシクロアルキル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基、フェノキシカルボニル基、或いは、−ＯＲ⁸、−ＳＲ⁹、−ＳＯＲ⁹、−ＳＯ₂Ｒ⁹若しくは−ＮＲ¹⁰Ｒ¹¹を示し、かつ、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷の少なくとも一つは、−ＯＲ⁸、−ＳＲ⁹、又は−ＮＲ¹⁰Ｒ¹¹を示す。
ただし、Ｒ⁸は、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜８のアルカノイル基、炭素数３〜１２のアルケニル基、炭素数３〜６のアルケノイル基、炭素数３〜１５のシクロアルキル基、フェニル基、−（ＣＨ₂ＣＨ₂Ｏ）_nＨ（ｎは１〜２０の整数）、又は炭素数３〜２０のアルキルシリル基を示す。
Ｒ⁹は、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数３〜１２のアルケニル基、炭素数３〜１５のシクロアルキル基、又はフェニル基を示す。
Ｒ¹⁰及びＲ¹¹は、互いに独立して、水素原子、或いは、それぞれ置換基を有していても良い、炭素数１〜１２のアルキル基、炭素数２〜１２のアルカノイル基、炭素数３〜６のアルケノイル基、炭素数３〜５のアルケニル基、炭素数５〜１２のシクロアルキル基、フェニル基、ベンゾイル基、又は、ビフェニル基を示す。フェニル基、ベンゾイル基、ビフェニル基は、置換されていても良い炭素数２〜８のアルキレン基を介して結合していても良い。
また、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、互いに結合し環構造を形成してもよい。〕 [Wherein, R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aminoalkyl group having 1 to 12 carbon atoms, or a substituent. Or an alkenyl group having 2 to 20 carbon atoms, or a group represented by the following general formula (IIa).

[Wherein, R ^{2 ″} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′,} and R ^{7 ′} each independently represent R ² in general formula (II) independently of that in general formula (II). ^′ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7, and * in the formula means bonding to a carbon atom in the general formula (II) at the portion *.
R ^{2 ′} each may have a substituent, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group. Indicates.
R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, carbon, which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 Represents an alkoxycarbonyl group, a phenoxycarbonyl group, or —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ^6. And at least one of R ⁷ represents —OR ⁸ , —SR ⁹ , or —NR ¹⁰ R ¹¹ .
However, R ⁸ is a hydrogen atom, or, respectively may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, carbon An alkenoyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a phenyl group, — (CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20), or alkylsilyl having 3 to 20 carbon atoms Indicates a group.
R ⁹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or phenyl. Indicates a group.
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or 3 to 3 carbon atoms, each optionally having a substituent. An alkenoyl group having 6 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzoyl group, or a biphenyl group; The phenyl group, benzoyl group, and biphenyl group may be bonded via an optionally substituted alkylene group having 2 to 8 carbon atoms.
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure. ]

  Further preferred compounds of the photopolymerization initiator (b) are compounds represented by the following general formula (III) or the following general formula (IV).

Wherein, R ¹ and R ^{2 'are} R ¹ and R ² in the general formula ^(II)' is synonymous with.
R ^{3 ″} , R ^{6 ″} and R ^{7 ″} each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 3 to 3 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 12 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A phenyl group, a benzoyl group or a biphenyl group may be bonded via an optionally substituted alkylene group having 2 to 8 carbon atoms.
R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 2 to 2 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 20 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A group, a phenoxycarbonyl group, an amide group or a nitro group; ]

[Wherein, R ¹ and R ^{2 ′} have the same meanings as R ¹ and R ^{2 ′ in} formula (II), respectively.
R ^{3 ″ ′} , R ^{6 ″ ′} and R ^{7 ″ ′} are independently of each other a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 An alkoxycarbonyl group or a phenoxycarbonyl group.
R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C20 alkanoyl group, C2-C2 12 alkoxycarbonyl groups, phenoxycarbonyl groups, amide groups or nitro groups are shown.
R ¹⁶ is a hydroxyl group, a thiol group, a nitro group, a cyano group, or a cycloalkenyl group having 3 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, or a carbon number, each optionally having a substituent. 6-18 aryl group, C2-C18 alkenyloxy group, C2-C18 alkenylthio group, acyl group, carboxyl group, acyloxy group, amino group, acylamino group, carbamate group, carbamoyl group, carboxylic acid An ester group, a sulfamoyl group, a sulfonic acid ester group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a tetrahydrothiophene dioxide group, or a trialkylsilyl group. ]

[B-1] substituent R ^2, preferably R ^{2 ′}
In the general formula (I), R ² is an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a benzoyl group, or an alkoxycarbonyl group having 2 to 10 carbon atoms. A group, a phenoxycarbonyl group, a C1-C20 heteroaryl group, a C1-C20 heteroaryloyl group, or a C1-C20 aminocarbonyl group. Each of these groups may be substituted.

R ² is preferably R ^{2 ′} in the general formula (II), and is an alkanoyl group having 2 to 8 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, A phenoxycarbonyl group; Each of these groups may be substituted.

  Here, specific examples of the alkanoyl group having 2 to 8 carbon atoms include propionyl group and butyryl group, and specific examples of the alkenoyl group having 4 to 6 carbon atoms include butenoyl group, pentenoyl group, hexenoyl group and the like. Specific examples of the alkoxycarbonyl group having 2 to 6 carbon atoms include an ethoxycarbonyl group and a butoxycarbonyl group.

R ² and R ^{2 ′} are more preferably an alkanoyl group having 2 to 5 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, and a phenoxycarbonyl group.

Any of the above-described substituents may further have a substituent described later in [b-11].
The “benzoyl group” defined for R ² includes one or more of —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ , and / or the substituent described in [b-11]. or also include those substituted by -NR ¹⁰ R ^11.

[B-2] Substituents X and Y In general formula (I), X and Y each independently represent an arbitrary substituent. The optional substituent is not particularly limited as long as it is a monovalent organic group.

Examples of the substituent for X include the substituents described in [b-11]. Among these, a 5-substituted phenyl group having R ^{3 to} R ⁷ in the general formula (II) as a substituent is preferable. Preferably, the substituent etc. which have cyclic structures, such as a carbazole skeleton and a thioxanthone skeleton, are mentioned.

  Moreover, as a substituent of Y, a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C1-C8 aminoalkyl group, and a substituent as described in [b-11]. Preferred are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and these groups are each substituted. Also good.

[B-3] Substituent R ¹
In General Formula (II), R ¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted aminoalkyl group having 1 to 12 carbon atoms, or an optionally substituted group. A good alkenyl group having 2 to 12 carbon atoms or a group represented by the following general formula (IIa) is shown.

[Wherein, R ^{2 ″} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′,} and R ^{7 ′} each independently represent R ² in general formula (II) independently of that in general formula (II). ^′ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7, and * in the formula means bonding to a carbon atom in the general formula (II) at the portion *.

R ¹ is preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted aminoalkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. And more preferably an optionally substituted aminoalkyl group having 1 to 8 carbon atoms.

  Here, specific examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group, and specific examples of the aminoalkyl group having 1 to 12 carbon atoms include an aminomethyl group and an aminoethyl group. Examples of the alkenyl group having 2 to 12 carbon atoms such as aminobutyl group include vinyl group, allyl group, and 1-propenyl group.

[B-4] Substituents R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷
In the general formula (II), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a C 1-12 alkyl group, preferably a C 1-8 alkyl group. An alkenoyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, preferably an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, and a benzyl group. , a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, 2 to 12 carbon atoms, preferably an alkoxycarbonyl group having 2 to 8 carbon atoms, or phenoxycarbonyl group 7-8 carbon atoms, -OR ^8, -SR ^9, -SOR ^9, -SO ₂ R ^9, or shows a -NR ¹⁰ R ^11, and at least one of ^{R 3, R 4, R 5} , R 6 and R ^7, -OR 8, -SR ⁹ or, indicates ^{-NR 10 R 11, R 3,} R 4, R 5, R 6 and R ⁷ Bound ring structure may be formed. Each of these groups may be substituted.

More preferably, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenoyl group having 3 to 5 carbon atoms, or a carbon number. 1 to 5 alkoxy groups, cycloalkyl groups having 5 to 6 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 5 carbon atoms, 7 to 10 carbon atoms Phenoxycarbonyl group, or —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ , or —NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ At least one represents —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure. is there.

  Here, specific examples of the alkoxy group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, include a methoxy group, an ethoxy group, and a butoxy group, and the cycloalkyl group having 5 to 8 carbon atoms includes a cyclohexyl group and a cyclohexane. A heptyl group, a cyclooctyl group, etc. are mentioned, and the other substituents correspond to the specific examples of [b-1] and [b-3].

  Any of the above-described substituents may further have a substituent described later in [b-11].

The “phenyl group” defined in R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is, in addition to the substituent described in [b-11], one or more —OR ⁸ , —SR ⁹ , -SOR ^9, also include those substituted by -SO ₂ R ^9, and / or -NR ¹⁰ R ^11.
In addition, —OR ⁸ , —SR ⁹ or —NR ¹⁰ R ¹¹ may be bonded to R ⁸ , R ⁹ , R ¹⁰ , and / or R ¹¹ to form a ring structure, and the ring structure is a 5-membered A ring and a 6-membered ring are preferable.

[B-5] Substituent R ⁸
R ⁸ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a phenyl group, an alkanoyl group having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms. , An alkenyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, preferably 5 to 8 carbon atoms, a phenyl group,-( CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20) or an alkylsilyl group having 3 to 20 carbon atoms, preferably 3 to 15 carbon atoms. Each of these groups may be substituted.

  Here, specific examples of the alkyl group having 1 to 12 carbon atoms substituted with a phenyl group include a phenylmethyl group, a phenylethyl group, and a phenylpropyl group. The carbon number is 3 to 20, and preferably 3 carbon atoms. Specific examples of the alkylsilyl group of -15 include propylsilyl group, butylsilyl group and the like, and other substituents are specific examples of [b-1], [b-3], and [b-4]. This is equivalent to

More preferably, R ⁸ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a phenyl group, an alkanoyl group having 2 to 4 carbon atoms, or an alkenyl having 3 to 6 carbon atoms. Group, an alkenoyl group having 3 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a phenyl group, — (CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20), or 3 to 12 carbon atoms. An alkylsilyl group is shown.

  Any of the above-described substituents may further have a substituent described later in [b-11].

In addition, the “alkyl group” defined in R ⁸ includes those substituted by one or more —OR ¹⁷ CN and —OR ¹⁸ (CO) OR ¹⁹ in addition to the substituent described in [b-11]. included.
R ¹⁷ and R ¹⁸ each independently represent an optionally substituted alkylene group having 1 to 4 carbon atoms, preferably an ethylene group, and R ¹⁹ has a substituent. Or an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

The “phenyl group” defined in R ⁸ includes those represented by the following formula (V) in addition to those substituted with the substituents described in [b-11].

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ and R ⁷ have the same meanings as those in the formula (II), respectively.
M ¹ is a direct bond, an ether group, a sulfide group, an alkylene group having 1 to 12 carbon atoms, a cycloalkenylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, a phenylene group, a biphenylene group, Terphenylene group, naphthylene group, —NR ¹⁰ —, — (CO) O—R ^17a —O (CO) —, — (CO) O— (CH ₂ CH ₂ O) m— (CO) — (m is 1 Or an integer above), — (CO) —R ^17b — (CO) —, an alkyleneoxy group having 1 to 12 carbon atoms, —R ^18a —S—, a piperazino group, or —R ^18b —NH—. These may be a plurality of combinations, each of which may have a substituent.
R ^17a and R ^17b are each independently an optionally substituted alkylene group having 2 to 12 carbon atoms, and R ^18a and R ^18b are each independently an ^optionally substituted carbon atom having 1 to 1 carbon atoms. 12 alkylene groups are shown. )

  Here, specific examples of the alkylene group having 1 to 12 carbon atoms include methylene, ethylene group, propylene group and the like, and specific examples of the cycloalkenylene group having 1 to 12 carbon atoms include a cyclopentenylene group, A cyclohexenylene group, and the like. Examples of the alkyleneoxy group having 1 to 12 carbon atoms include a methyleneoxy group and an ethyleneoxy group. Other substituents include [b-1] and [b-3. ] And [b-4] are given as specific examples.

[B-6] Substituent R ⁹

R ⁹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or phenyl. Preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a phenyl group, an alkenyl group having 3 to 8 carbon atoms, or a cyclohexane having 5 to 8 carbon atoms. It is an alkyl group or a phenyl group, and each of these groups may be further substituted.

R ⁹ is more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 12 carbon atoms substituted with a phenyl group, an alkenyl group having 3 to 4 carbon atoms, or a carbon atom having 5 to 6 carbon atoms. A cycloalkyl group or a phenyl group, each of which may be further substituted.

The “alkyl group” defined for R ⁹ includes those substituted with one or more —OR ¹⁷ CN and —OR ¹⁸ (CO) OR ¹⁹ in addition to the substituents described in [b-11]. It is.
R ¹⁷ and R ¹⁸ each independently represent an optionally substituted alkylene group having 1 to 4 carbon atoms, preferably an ethylene group, and R ¹⁹ represents an optionally substituted carbon atom having 1 to 1 carbon atoms. 8, preferably an alkyl group having 1 to 4 carbon atoms.

Further, the “phenyl group” defined in R ⁹ includes those represented by the above formula (V) in addition to those substituted with the substituent described in [b-11].
In addition, as for each substituent, what was mentioned as a specific example of [b-1], [b-3], [b-4] is corresponded.

[B-7] Substituents R ¹⁰ and R ¹¹ R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, each of which may have a substituent, An alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzoyl group, or a biphenyl group; Preferably, independently of each other, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, and 5 carbon atoms -8, a cycloalkyl group, a phenyl group, a benzoyl group or a biphenyl group. The phenyl group, benzoyl group, or biphenyl group may be bonded via an alkylene group having 2 to 8 carbon atoms, and the alkylene group having 2 to 8 carbon atoms may be further substituted. Examples of the substituent which may be substituted include any organic group described in [b-11]. More preferably, the alkyl group having 1 to 8 carbon atoms is unsubstituted or substituted with a hydroxyl group, an alkoxy group, or a phenyl group.

More preferably, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkenoyl group having 3 to 4 carbon atoms, or 3 to 3 carbon atoms. 4 an alkenyl group, a cycloalkyl group having 5 to 6 carbon atoms, a phenyl group, a benzoyl group or a biphenyl group. The phenyl group, benzoyl group, or biphenyl group may be bonded via an alkylene group having 2 to 8 carbon atoms, and the alkylene group having 2 to 8 carbon atoms may be further substituted. Examples of the substituent which may be substituted include any organic group described in [b-11]. More preferably, the alkyl group having 1 to 8 carbon atoms is unsubstituted or substituted with a hydroxyl group, an alkoxy group, or a phenyl group.

The “phenyl group” defined in R ¹⁰ includes those represented by the above formula (V) in addition to those substituted by the substituent described in [b-11].

  In addition, the specific example of each substituent corresponds to what was mentioned as a specific example of [b-1], [b-3], [b-4].

[B-8] Substituents R ^{3 "} , R ^6" , R ^{7 "} , R ^3"' , R ^{6 "'} and R ^7"' R ^{3 "} , R ^6" , R ^{7 "} , R ^3"' , R ^{6 ″ ′} and R ^{7 ″ ′} are independently of each other a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 3 to 12 carbon atoms. Alkenoyl group, alkoxy group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms Or a phenoxycarbonyl group, preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenoyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, carbon A cycloalkyl group having a number of 5 to 8, phenyl group, benzyl group, benzoyl group, charcoal Number 2-8 alkanoyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a phenoxycarbonyl group having 7 to 10 carbon atoms. Each of these groups may be substituted with an arbitrary substituent.

R ^{3 ″} , R ^{6 ″} , R ^{7 ″} , R ^{3 ″ ′} , R ^{6 ″ ′} and R ^{7 ″ ′} are more preferably independently of each other a hydrogen atom, a halogen atom, or a C 1-6 alkyl. Group, alkenoyl group having 3 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 6 carbon atoms, carbon number A 2-6 alkoxycarbonyl group or a C7-8 phenoxycarbonyl group is shown, and these groups may each be substituted.

  In addition, the specific example of each substituent corresponds to what was mentioned as a specific example of [b-1], [b-3], [b-4].

[B-9] Substituents R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, or 2 carbon atoms. -12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C20 alkanoyl group, C2-C12 alkoxy A carbonyl group, a phenoxycarbonyl group, an amide group or a nitro group, preferably, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenoyl group having 3 to 8 carbon atoms, carbon C 1-8 alkoxy group, C 5-8 Roarukiru group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or phenoxycarbonyl group having 7 to 10 carbon atoms. Each of these groups may be substituted with an arbitrary substituent.

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} are more preferably independently of each other a hydrogen atom, a halogen atom, or a carbon number of 1-6. Alkyl group, alkenoyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, cycloalkyl group having 5 to 6 carbon atoms, phenyl group, benzyl group, benzoyl group, alkanoyl group having 2 to 6 carbon atoms, carbon A C2-C6 alkoxycarbonyl group or a C7-C8 phenoxycarbonyl group is shown, and these groups may each be substituted.

  In addition, the specific example of each substituent corresponds to what was mentioned as a specific example of [b-1], [b-3], [b-4].

[B-10] Substituent R ¹⁶ R ¹⁶ is a hydroxyl group, thiol group, nitro group, cyano group, cycloalkenyl group having 3 to 18 carbon atoms, alkylthio group having 1 to 18 carbon atoms, or 6 to 18 carbon atoms. Aryl group, alkenyloxy group having 2 to 18 carbon atoms, alkenylthio group having 2 to 18 carbon atoms, acyl group, carboxyl group, acyloxy group, amino group, acylamino group, carbamate group, carbamoyl group, carboxylic acid ester group, A sulfamoyl group, a sulfonate group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a tetrahydrothiophene dioxide group, or a trialkylsilyl group. Each of these groups may be substituted with an arbitrary substituent.

  Here, specific examples of the cycloalkenyl group having 3 to 18 carbon atoms include a cyclopentenyl group and a cyclohexenyl group. Specific examples of the alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, n -Propylthio group and the like, specific examples of the aryl group having 6 to 18 carbon atoms include phenyl group, tolyl group, xylyl group and the like, and specific examples of the alkenyloxy group having 2 to 18 carbon atoms include propenyl. An oxy group, a hexenyloxy group, etc. are mentioned, As a specific example of a C2-C18 alkenylthio group, a vinylthio group, a propenylthio group, a hexenylthio group etc. are mentioned.

[B-11] Substituents that may be substituted respectively In the chemical formulas (I) to (IV) according to the present invention, R ^{1 to} R ¹⁶ , R ^{2 ′ to} R ^{7 ′} , R ^{2 ″ to} R ^{7 “} , R ^{3 ″ ′} , R ^{6 ″ ′} , R ^{7 ″ ′} , R ^{12 to} R ¹⁶ , and R ^{12 ′ to} R ^{16 ′} are each independently an optionally substituted fluorine. A halogen atom such as an atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxyl group; a thiol group; a nitro group; a cyano group; any organic group.

As an arbitrary organic group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group, n-heptyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as n-octyl group and t-octyl group; a cyclohexane having 3 to 18 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group Alkyl group; linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group and hexenyl group; cycloalkenyl group having 3 to 18 carbon atoms such as cyclopentenyl group and cyclohexenyl group; methoxy group and ethoxy group Group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-a A linear or branched alkoxy group having 1 to 18 carbon atoms such as a ruoxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octyloxy group; methylthio group, ethylthio group, n- Propylthio group, isopropylthio group, n-butylthio group, s-butylthio group, t-butylthio group, amylthio group, t-amylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, t-octylthio group, etc. A linear or branched alkylthio group having 1 to 18 carbon atoms; an aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group, and mesityl group; 7 to 18 carbon atoms such as benzyl group and phenethyl group Aralkyl group; linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyloxy group, propenyloxy group, hexenyloxy group, etc. Shi group; represented by -OCOR ^21; carboxyl group; an acyl group represented by -COR ^20; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group a carbamoyl group represented by -CONR ²⁶ R ^27;; carbamate group represented by -NHCOOR ^25; acylamino group represented by -NHCOR ^24; amino group represented by -NR ²² R ^23; acyloxy group -COOR ²⁸ A sulfamoyl group represented by —SO ₃ NR ²⁹ R ³⁰ ; a sulfonic acid ester group represented by —SO ₃ R ³¹ ; a 2-thienyl group, a 2-pyridyl group, a furyl group, Such as oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group Examples thereof include a saturated or unsaturated heterocyclic group and a trialkylsilyl group such as a trimethylsilyl group.

R ^{20 to} R ³¹ are each a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. To express. These positional relationships are not particularly limited, and when they have a plurality of substituents, they may be the same type or different.

In addition, examples of the substituent of the present invention include substituents such as ═N—OC (═O) R ² (wherein R ² has the same meaning as in formula (I)). It is done. As such a compound, R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number having 2 to 20 carbon atoms, which is substituted with ═N—OC (═O) R ² . It may be an alkanoyl group, a benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group or phenoxycarbonyl group having 2 to 12 carbon atoms, or an amide group.

In the above, the substituent may have not only one but also the same type and / or a plurality of substituents, or a plurality of substituents may be bonded to each other to form a ring. The ring may be a saturated or unsaturated aromatic ring or heterocyclic ring, and each of these rings may further have a substituent, and the substituent may further form a ring.
The following structures are mentioned as a preferable cyclic structure.

（ここで、ＺはＯ、Ｓ、Ｎ，ＳＯ₂、又は−（Ｃ＝Ｏ）−を示し、Ｒは［ｂ−１０］に説明したＲ¹⁶に同義である。）

(Here, Z represents O, S, N, SO ₂ , or — (C═O) —, and R has the same meaning as R ¹⁶ described in [b-10].)

  Specific examples of preferred compounds of the present invention are shown below. In the following, Me represents a methyl group.

  The molecular weight of the compound represented by the general formula (I), preferably the general formula (II), more preferably the general formula (III) or (IV) depends on the balance between volatility, bleedout and solvent solubility. When it has, it is 100-2000 normally including the substituent, Preferably it is 150-1500, More preferably, it is 200-1000.

  Below, the general synthesis | combining method of the compound represented with general formula (I) of this invention is shown.

Here, Q represents a 5-substituted phenyl group having R ^{3 to} R ⁷ in the general formula (II) as a substituent, a substituent having a cyclic structure such as a carbazole skeleton or a thioxanthone skeleton, and Ra and Rb are an alkyl group, An alkanoyl group, an alkenoyl group, an alkenyl group, an alkoxy group, a benzoyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, a cycloalkyl group, a phenyl group (these may be substituted respectively), etc., and Rc is a monovalent organic Indicates a group.

  The composition for forming a hologram recording layer of the present invention is represented by the general formula (I), preferably the general formula (II), more preferably the general formula (III) or (IV) as the photopolymerization initiator (b). Any of these compounds may be used alone, or two or more of these compounds may be used in any combination and ratio.

(Optional component of photopolymerization initiator)
As the photopolymerization initiator of the component (b) constituting the hologram recording layer forming composition of the present invention, a photopolymerization initiator composed of the compound represented by the general formula (I) can be used alone. If necessary, other photopolymerization initiators can be used in combination.

  Other photopolymerization initiators include, for example, acetophenones, benzophenones, hydroxybenzenes, thioxanthones, anthraquinones, ketals, hexaarylbiimidazoles, titanocenes, acylphosphine oxides, halogenated hydrocarbon derivatives , Organoborates, organic peroxides, onium salts, sulfone compounds, carbamic acid derivatives, sulfonamides, triarylmethanols, and the like.

  One of these other photopolymerization initiators may be used alone, or two or more thereof may be used in any combination and ratio.

<Resin matrix (c)>
The composition for forming a hologram recording layer of the present invention preferably further contains a resin matrix (c). As the resin matrix (c), a resin that can be dissolved in a solvent may be used, or a resin that is three-dimensionally cross-linked may be used.

  Resins that can be dissolved in the solvent include chlorinated polyethylene, polymethyl methacrylate, copolymers of methyl methacrylate and other alkyl acrylates, copolymers of vinyl chloride and acrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl Formal, polyvinyl butyral, polyvinyl pyrrolidone, ethyl cellulose, acetyl cellulose and the like can be mentioned. Of these, polymethyl methacrylate is preferred.

  The three-dimensional crosslinked resin matrix is insoluble in a solvent and contains a reaction cured product of a polymerizable compound that is liquid at room temperature and a compound that is reactive to the polymerizable compound. Since the three-dimensional cross-linked resin matrix becomes a physical obstacle, volume change during recording is suppressed. That is, in the recording layer after recording, the bright part expands and the dark part contracts, and the surface of the hologram optical recording medium becomes uneven. In order to suppress this volume change, it is more preferable to use a three-dimensional crosslinked resin matrix for the recording layer.

  Examples of reactions that can be used to form a three-dimensional crosslinked resin matrix include, but are not limited to, cationic epoxy polymerization, cationic vinyl ether polymerization, cationic alkenyl ether polymerization, cationic allene ether polymerization, cationic ketene acetal polymerization. , Epoxy-amine addition polymerization, epoxy-thiol addition polymerization, unsaturated ester-amine addition polymerization (by Michael addition), unsaturated ester-thiol addition polymerization (by Michael addition), vinyl-silicon hydride addition polymerization (hydrosilylation), Examples include isocyanate-hydroxyl addition polymerization (urethane formation), isocyanate-thiol addition polymerization, and isocyanate-amine addition polymerization (urea formation).

The above reaction is enabled or facilitated by a suitable catalyst. For example, cationic epoxy polymerization occurs rapidly at room temperature using a catalyst based on BF ₃ , other cationic polymerization proceeds in the presence of protons, and the epoxy-mercaptan reaction and Michael addition are promoted by a base such as an amine. Hydrosilylation proceeds rapidly due to the presence of a transition metal catalyst such as platinum, and urethane and urea formation proceeds rapidly when a tin catalyst is used.

Among these, an isocyanate-hydroxyl addition reaction, an isocyanate-amine addition reaction, an isocyanate-thiol addition reaction, an epoxy-amine addition reaction, and an epoxy-thiol addition reaction that can be cross-linked at an appropriate temperature and time are preferable. .
Hereinafter, raw material compounds that can be used in these reactions will be described.

-Polyisocyanate The polyisocyanate that can be used in the isocyanate-hydroxyl reaction, isocyanate-amine reaction, and isocyanate-thiol reaction is not particularly limited as long as it has two or more isocyanate groups in one molecule. The number of isocyanate groups in one molecule is not particularly limited as long as it is usually 2 or more. If the number of isocyanate groups is small, the hardness required for the matrix may not be obtained. On the other hand, the upper limit of the number of isocyanate groups is not particularly limited, but is usually preferably 5 or less. If many isocyanate groups remain in the matrix, the storage stability of the matrix may be deteriorated.

  Examples of polyisocyanates that can be used in the isocyanate-hydroxyl reaction, isocyanate-amine reaction, and isocyanate-thiol reaction include aliphatic isocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and isophorone. Alicyclic isocyanates such as diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane; tolylene-2,4-diisocyanate, tolylene-2,5-diisocyanate, tolylene-2 Fragrance such as 1,6-diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene-1,5'-diisocyanate Isocyanates; and the like multimers thereof. Among them, 3-7 mers are preferred. Moreover, the reaction material with polyhydric alcohols, such as water, a trimethylol ethane, a trimethylol propane, etc. are mentioned. Among these, tolylene diisocyanate, hexamethylene diisocyanate, and multimers thereof, or derivatives thereof are particularly preferable. Also, polyisocyanates (prepolymers) having a polyfunctional terminal isocyanate group can be used by reacting the above isocyanates with a compound having two or more active hydrogens in the molecule. Compounds having two or more active hydrogens in the molecule include ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, polyethylene glycol, polytetramethylene glycol, ethylenediamine, isophoronediamine, 4 , 4′-diaminodicyclohexylmethane, polyols described below, and the like can be used.

  The average molecular weight of the polyisocyanate is preferably from 100 to 50,000 in terms of number average, more preferably from 150 to 10,000, and even more preferably from 150 to 5,000. If the molecular weight is less than 100, the crosslink density increases, so that the hardness of the matrix becomes too high, and the recording speed may decrease. On the other hand, if it exceeds 10,000, the compatibility with other components may decrease, or the crosslinking density may decrease, so that the hardness of the matrix may be too low and the recorded content may be lost.

  In addition, the polyisocyanate may contain components other than an isocyanate group in the range which does not impair the effect of this invention remarkably.

-Polyol The kind of polyol that can be used in the isocyanate-hydroxyl reaction is not particularly limited as long as it has two or more hydroxyl groups in one molecule. The number of hydroxyl groups in one molecule is not particularly limited as long as it is usually 2 or more. If the number of hydroxyl groups is small, the hardness required for the matrix may not be obtained. On the other hand, the upper limit of the number of hydroxyl groups is not particularly limited, but is usually preferably 5 or less. If many hydroxyl groups remain in the matrix, the hygroscopicity of the matrix becomes high, which may affect the storage stability of the record.

  Examples of polyols that can be used in the isocyanate-hydroxyl reaction include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. , Neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, polyethylene glycol, polytetramethylene glycol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyether polyol, etc. There is.

  The average molecular weight of the polyol is preferably from 100 to 50,000 in terms of number average, more preferably from 150 to 10,000, and even more preferably from 150 to 5,000. If the molecular weight is less than 100, the crosslink density increases, so that the hardness of the matrix becomes too high, and the recording speed may decrease. On the other hand, if it exceeds 50,000, the compatibility with other components may be lowered, or the crosslinking density may be lowered, so that the hardness of the matrix becomes too low and the recorded content may be lost.

-Epoxy The epoxy compound that can be used for the epoxy-amine reaction and epoxy-thiol reaction is not particularly limited as long as it has two or more epoxy groups in one molecule. The number of epoxy groups in one molecule is not particularly limited as long as it is usually 2 or more. If the number of epoxy groups is small, the hardness required for the matrix may not be obtained. On the other hand, the upper limit of the number of epoxy groups is not particularly limited, but is usually preferably 5 or less. If many epoxy groups remain in the matrix, the storage stability of the record may be affected.

  Examples of compounds having two or more epoxy groups in one molecule include polyglycidyl ethers of polyols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, trimethylolpropane, and glycerin. 4-7 membered ring such as compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, etc. Examples thereof include alicyclic epoxy compounds having a cycloaliphatic group, bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol or cresol novolak type epoxy compounds.

  The average molecular weight of the compound having an epoxy group is preferably 100 or more and 50000 or less, more preferably 150 or more and 10,000 or less, and still more preferably 150 or more and 5000 or less in terms of number average. If the molecular weight is less than 100, the crosslink density increases, so that the hardness of the matrix becomes too high, and the recording speed may decrease. On the other hand, if it exceeds 50,000, the compatibility with other components may be lowered, or the crosslinking density may be lowered, so that the hardness of the matrix becomes too low and the recorded content may be lost.

-Amine Examples of compounds that can be used in the isocyanate-amine addition reaction and epoxy-amine addition reaction are not particularly limited as long as they have two or more amino groups in one molecule.

  Examples of compounds having two or more amino groups in one molecule include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, isophoronediamine, menthanediamine, 4,4′-diaminodicyclohexylmethane, etc. And aromatic amines such as m-xylylenediamine, diaminodiphenylmethane, and m-phenylenediamine.

  The average molecular weight of the compound having an amino group is preferably from 100 to 50,000, more preferably from 150 to 10,000, and even more preferably from 150 to 5,000 in terms of number average. If the molecular weight is less than 100, the crosslink density increases, so that the hardness of the matrix becomes too high, and the recording speed may decrease. On the other hand, if it exceeds 50,000, the compatibility with other components may be lowered, or the crosslinking density may be lowered, so that the hardness of the matrix becomes too low and the recorded content may be lost.

-Thiol As an example of the compound which can be used for the isocyanate-thiol addition reaction and the epoxy-thiol addition reaction, the kind thereof is not particularly limited as long as it has two or more thiol groups in one molecule.

  Examples of compounds having two or more thiol groups in one molecule include 1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,2-benzenedithiol, 1,3-butanedithiol, Examples include benzenedithiol, 1,4-benzenedithiol, 1,10-decanedithiol, 1,2-ethanedithiol, 1,6-hexanedithiol, 1,9-nonanedithiol, and the like.

  In the composition for forming a hologram recording layer of the present invention, any one kind of the resin matrix (c) may be used alone, or two or more kinds may be used in any combination and ratio.

<Combination ratio>
The content of the polymerizable photoactive compound (a) in the composition for forming a hologram recording layer of the present invention is usually 0.5% by weight or more, particularly 1% by weight or more, based on the component (c). Usually, it is preferably 100% by weight or less, particularly preferably 50% by weight or less. If the content of the photoactive compound (a) is too small, the change in refractive index is small and the recording efficiency may be lowered. On the other hand, if the amount of the photoactive compound (a) used is too large, a large amount of unreacted photoactive compound remains, which may cause bleed out when used as a recording material.

  The content of the photopolymerization initiator (b) in the composition for forming a hologram recording layer of the present invention is usually 0.1 weight with respect to the total of the components (a), (b) and (c). % Or more, particularly 0.5% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less. If the content of the photopolymerization initiator (b) is too small, the amount of radicals generated is reduced, so that the rate of photopolymerization becomes slow and the hologram recording sensitivity may be lowered. On the other hand, if the amount of the photopolymerization initiator (b) used is too large, radicals generated by light irradiation recombine with each other or disproportionate, so that the contribution to photopolymerization is reduced. Sensitivity may decrease. When two or more photopolymerization initiators (b) are used in combination, the total amount thereof satisfies the above range.

  In particular, the composition for forming a hologram recording layer of the present invention contains the compound represented by the general formula (I), preferably the general formula (II), more preferably the general formula (III) or (IV). The amount is usually 0.01% by weight or more, especially 0.1% by weight or more, and usually 10% by weight or less, especially 5%, based on the total of the components (a), (b) and (c). It is preferable to set it as the range of weight% or less. If this content is too small, the amount of radicals generated will be small, so that the rate of photopolymerization will be slow and the hologram recording sensitivity may be low. On the other hand, if too much, radicals generated by light irradiation recombine with each other or disproportionate, so that the contribution to photopolymerization is reduced, and the hologram recording sensitivity may also be lowered.

  The content of the resin matrix (c) in the composition for forming a hologram recording layer of the present invention is usually 10% by weight or more based on the total of the components (a), (b) and (c). It is preferably 50% by weight or more, more preferably 70% by weight or more, and usually 99.9% by weight or less, especially 98% by weight or less. When the content of the resin matrix (c) is too small, the shape retention of the matrix becomes small, and when it is too large, the content of the photoactive compound decreases and it becomes difficult to output a signal.

<Other ingredients>
In addition, the composition for forming a hologram recording layer of the present invention includes the photoactive compound (a) having the above-described polymerizability, a photopolymerization initiator (b), and a resin matrix (c) as long as not departing from the spirit of the present invention. In addition, other components may be contained.

  For example, with respect to hologram recording, it is important to control the photoreaction that occurs in the bright part during recording, so it is preferable to add an additive that can control the polymerization. Additives capable of controlling the polymerization include compounds having a terpenoid skeleton, cyclic having at least two or more double bonds, and the positions of the double bonds in the relative positions 1, 4 or non- Examples include cyclic compounds, allyl compounds, mercapto compounds, amine compounds, and phenols.

  Further, the composition for forming a hologram recording layer of the present invention may contain any additive as required for controlling the excitation wavelength and excitation energy of the sensitizer, controlling the reaction, improving the characteristics, etc. it can.

Examples of the additive include the following compounds.
Examples of the compound that controls excitation of the sensitizer include a sensitizer and a sensitizer.
As a sensitizer, it can be arbitrarily selected from various known sensitizers, and depending on the wavelength of the laser beam used for recording and the type of initiator used, a green laser is used. In the case of the system used, specific examples of preferable sensitizers include compounds described in JP-A-5-241338, JP-A-2-69, JP-B-2-55446, and the like. In the case of a system to be used, JP-A No. 2000-10277, JP-A No. 2004-198446, JP-A No. 2005-62415, JP-A No. 2005-91593, JP-A No. 2004-191938, JP-A No. 2004-2004. No. 272212, JP-A No. 2004-221958, JP-A No. 2004-252421, JP-A No. 2005-107191, JP-A No. 2004-264834 Compounds described in such publications can be mentioned. Any of the various sensitizers exemplified above may be used alone, or two or more may be used in any combination and ratio.

Examples of the compound used for controlling the reaction include a polymerization initiator, a chain transfer agent, a polymerization terminator, a compatibilizing agent, a reaction auxiliary agent, and the like.
Other examples of additives that may be required for improving the properties include dispersants, antifoaming agents, plasticizers, preservatives, stabilizers, and antioxidants.
Any one of these additives may be used alone, or two or more thereof may be used in any combination and ratio.

  The amount of these additives used is usually a ratio of 0.001% by weight or more, especially 0 in terms of the ratio of the component (a), the component (b) and the component (c) of the composition for forming a hologram recording layer of the present invention. 0.01% by weight or more, and usually 30% by weight or less, preferably 10% by weight or less. When two or more additives are used in combination, the total amount thereof is set to satisfy the above range.

The hologram recording material of the present invention uses the composition for forming a hologram recording layer of the present invention.
The hologram recording material of the present invention may consist only of the composition for forming a hologram recording layer of the present invention, or may contain other components. Although there is no restriction | limiting in particular in another component, As an example, various additives, such as a light dispersing agent and a coloring material, are mentioned. The content of other components is arbitrary as long as the effects of the present invention are not significantly impaired.

  Further, the hologram recording layer forming composition and the hologram recording material of the present invention can three-dimensionally record interference fringes caused by light interference, and can be used for volume hologram type optical recording media. Is preferred.

[II. Hologram optical recording medium]
The hologram optical recording medium of the present invention includes at least a layer containing the above-described hologram recording material of the present invention.

  The layer containing the hologram recording material of the present invention is arbitrary, but is usually a layer on which information is recorded (this is referred to as “recording layer”).

  There is no restriction | limiting in the other specific structure in the hologram optical recording medium of this invention, It is arbitrary. Hereinafter, a hologram optical recording medium according to an embodiment of the present invention (this may be referred to as “optical recording medium of the present embodiment”) will be described in detail.

  The optical recording medium of this embodiment is configured to include at least a recording layer formed using the hologram recording material of the present invention. Further, the optical recording medium of the present embodiment includes a support and other layers as necessary.

  The recording layer is a layer on which information is recorded. Information is usually recorded as a hologram. In the optical recording medium of this embodiment, the recording layer is not particularly limited as long as it is formed using the hologram recording material of the present invention.

  The thickness of the recording layer is not particularly limited and may be appropriately determined in consideration of the recording method and the like. Generally, it is usually 1 μm or more, preferably 10 μm or more, and usually 1 cm or less, preferably 2000 μm or less. It is a range. If the recording layer is too thick, the selectivity of each hologram is lowered during multiplex recording on the optical recording medium, and the degree of multiplex recording may be reduced. If the recording layer is too thin, it is difficult to uniformly form the entire recording layer, and it may be difficult to perform multiplex recording with uniform diffraction efficiency of each hologram and a high S / N ratio.

  Usually, the optical recording medium has a support, and the recording layer and other layers are laminated on the support to constitute the optical recording medium. However, when the recording layer or other layers have the required strength and durability, the optical recording medium may not have a support.

The support is not particularly limited in detail as long as it has the required strength and durability, and any support can be used.
Specifically, although there is no restriction | limiting in the shape of a support body, Usually, it forms in flat form or a film form.

  Moreover, there is no restriction | limiting in the material which comprises a support body, Transparent or opaque may be sufficient. Examples of transparent materials for the support include organic materials such as acrylic, polyethylene terephthalate, polyethylene naphthoate, polycarbonate, polyethylene, polypropylene, amorphous polyolefin, polystyrene, and cellulose acetate; and inorganic materials such as glass, silicon, and quartz. It is done. Among these, polycarbonate, acrylic, polyester, amorphous polyolefin, glass and the like are preferable, and polycarbonate, acrylic, amorphous polyolefin, and glass are particularly preferable.

  On the other hand, when the opaque material is cited as a material on the support, a metal such as aluminum; a metal such as gold, silver, or aluminum, or a dielectric such as magnesium fluoride or zirconium oxide is coated on the transparent support. And the like.

  Although there is no restriction | limiting in particular also in the thickness of a support body, Usually, it is preferable to set it as the range of 0.1 mm or more and 1 mm or less. If the support is too thin, the mechanical strength of the optical recording medium may be insufficient and the substrate may be warped. If the support is too thick, the amount of transmitted light may be reduced and the cost may be increased.

  Moreover, you may surface-treat on the surface of a support body. This surface treatment is usually performed to improve the adhesion between the support and the recording layer. Examples of the surface treatment include subjecting the support to corona discharge treatment or forming an undercoat layer on the support in advance. Here, examples of the composition of the undercoat layer include halogenated phenols, partially hydrolyzed vinyl chloride-vinyl acetate copolymers, polyurethane resins, and the like.

  Furthermore, the surface treatment may be performed for purposes other than the improvement of adhesiveness. Examples thereof include a reflective coating treatment for forming a reflective coating layer made of a metal such as gold, silver, and aluminum; a dielectric coating treatment for forming a dielectric layer such as magnesium fluoride and zirconium oxide, and the like. It is done. These layers may be formed as a single layer or two or more layers.

  Further, the support may be provided only on either the upper side or the lower side of the recording layer of the optical recording medium of the present invention, or may be provided on both. However, when providing a support on both the upper and lower sides of the recording layer, at least one of the supports is configured to be transparent so as to transmit active energy rays (excitation light, reference light, reproduction light, etc.).

  In the case of an optical recording medium having a transparent support on one side or both sides of the recording layer, a transmissive or reflective hologram can be recorded. When a support having reflection characteristics on one side is used, a reflection type hologram can be recorded.

  Furthermore, patterning for data addresses may be provided on the support. There is no limitation on the patterning method in this case, but for example, irregularities may be formed on the support itself, a pattern may be formed on the reflective layer (described later), or a combination of these may be formed. Good.

  In addition to the recording layer and the support described above, other layers may be provided on the optical recording medium of the present embodiment. Examples of other layers include a protective layer, a reflective layer, an antireflection layer (antireflection film), and the like.

  The protective layer is a layer for preventing adverse effects such as a decrease in sensitivity due to oxygen and moisture and a deterioration in storage stability. There is no restriction | limiting in the specific structure of a protective layer, It is possible to apply a well-known thing arbitrarily. For example, a layer made of a water-soluble polymer, an organic / inorganic material, or the like can be formed as a protective layer.

  The reflective layer is formed when the optical recording medium is configured to be reflective. In the case of a reflective optical recording medium, the reflective layer may be formed between the support and the recording layer, or may be formed on the outer surface of the support. Usually, the support and the recording layer are used. It is preferable to be between.

  Further, in any of the transmission type and reflection type optical recording media, an antireflection film may be provided on the side on which recording light and readout light enter and exit, or between the recording layer and the support. The antireflection film functions to improve light utilization efficiency and suppress the generation of ghost images.

  There is no particular limitation on the method of manufacturing the optical recording medium of the present embodiment, and it can be manufactured by any method. As an example, the hologram recording material of the present invention can be produced by coating a support without a solvent and forming a recording layer. At this time, any method can be used as a coating method. Specific examples include spray method, spin coating method, wire bar method, dipping method, air knife coating method, roll coating method, blade coating method, doctor roll coating method and the like.

  In addition, when forming a recording layer having a particularly large thickness, recording is performed using a method in which the hologram recording material of the present invention is put into a mold and a method in which the hologram recording material is coated on a release film and punched out. Layers can also be formed.

  Alternatively, the hologram recording material of the present invention may be mixed with a solvent to prepare a coating solution, which may be coated on a support and dried to form a recording layer. Also in this case, any method can be used as a coating method. As an example, a method similar to the above-described coating method may be mentioned.

  The type of the solvent is not particularly limited, but it is usually preferable to use a solvent that has sufficient solubility for the components used, gives good coating properties, and does not attack the support.

Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, and propanol; diacetone alcohol, 3-hydroxy-3-methyl Ketone solvents such as 2-butanone; ether solvents such as tetrahydrofuran and dioxane; halogen solvents such as dichloromethane and chloroform; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol Propylene glycol solvents such as monomethyl ether and propylene glycol monoethyl ether; ester solvents such as ethyl acetate and butyl acetate; tetrafluoropropanol, octaf Perfluoroalkyl alcohol solvents such as olopentanol; highly polar solvents such as dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide; chain hydrocarbon solvents such as n-hexane and n-octane; cyclohexane and methylcyclohexane A cyclic hydrocarbon solvent; or a mixed solvent thereof.
In addition, any one of these solvents may be used alone, or two or more thereof may be used in any combination and ratio.

  Moreover, there is no restriction | limiting in particular also in the usage-amount of a solvent. However, the amount of solvent used should be adjusted so that the solid content concentration of the coating solution is 1% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight, from the viewpoint of coating efficiency and handling properties. Is preferred.

  Furthermore, when the hologram recording material of the present invention has a small amount of volatile components, the hologram recording material of the present invention can be produced by molding, for example, by an injection molding method or a hot press method. In this case, when the molded body has sufficient thickness, rigidity, strength, etc., the molded body can be used as it is as the optical recording medium of the present embodiment.

  Further, the recording layer made of the hologram recording material of the present invention may be produced by molding the above resin matrix (c) into a desired shape and then impregnating it with a photoactive compound, other additives and the like.

  The optical recording medium of the present embodiment manufactured by the above procedure can take the form of a self-supporting slab or a disk, and can be used for applications such as a three-dimensional image display device, a diffractive optical element, and a large capacity memory.

  Both writing (recording) and reading (reproducing) information on the optical recording medium of the present embodiment are performed by light irradiation.

  First, at the time of recording information, light capable of causing polymerization and concentration change of a polymerizable photoactive compound is used as object light (also called recording light). In particular, in the optical recording medium of the present embodiment, in order to record information as a hologram, the object light is irradiated onto the recording layer together with the reference light so that the object light and the reference light interfere with each other in the recording layer. As a result, the interference light causes polymerization and concentration change of the photoactive compound in the recording layer, and as a result, the interference fringes cause a refractive index difference in the recording layer, and the interference recorded in the recording layer. The fringes are recorded as holograms on the recording layer.

  On the other hand, when reproducing a hologram recorded on the recording layer, the recording layer is irradiated with predetermined reproduction light (usually reference light). The irradiated reproduction light is diffracted according to the interference fringes. Since the diffracted light contains the same information as the recording layer, the information recorded on the recording layer can be reproduced by reading the diffracted light with an appropriate detection means.

Note that the wavelength range of the recording light, the reproduction light, and the reference light is arbitrary depending on each application, and may be the visible light region or the ultraviolet region. Among these lights, for example, solid lasers such as ruby, glass, Nd-YAG, Nd-YVO ₄ ; diode lasers such as GaAs, InGaAs, GaN; helium-neon, argon, krypton, excimer, Gas lasers such as CO ₂ ; lasers excellent in monochromaticity and directivity, such as dye lasers having pigments.

Further, there is no limitation on the irradiation amount of the recording light, the reproduction light, and the reference light, and the irradiation amount is arbitrary as long as the recording and reproduction can be performed. However, if the amount is extremely small, the chemical change of the photoactive compound may be incomplete, and the heat resistance and mechanical properties of the recording layer may not be sufficiently expressed. The hologram recording material of the invention may be deteriorated. Therefore, the recording light, the reproduction light and the reference light are usually 1 mJ / cm ² or more in accordance with the composition of the hologram recording material of the present invention used for forming the recording layer, the kind of polymerization initiator, the blending amount, and the like. Irradiate within a range of 20 J / cm ² or less.

  The hologram recording system includes a polarization collinear hologram recording system, a reference light incident angle multiplexing type hologram recording system, etc., and any recording is possible when the composition for forming a hologram recording layer of the present invention is used as a recording medium. Even with this method, it is possible to provide good recording quality.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Example 1]
<Synthesis of photopolymerization initiator>

  2-acetylthioxanthone (12.7 g, 50 mmol) and p-isobutylbenzaldehyde (8.1 g, 50 mmol) were dissolved in 50 ml of ethanol. Next, potassium hydroxide (1.2 g, 20 mmol) was added and reacted for 4 hours under ethanol reflux. The reaction mixture was poured into 300 ml of ice water, 300 ml of ethyl acetate was further added, and the organic layer was separated. The extract was washed once with 300 ml of saturated brine and the organic layer was dried over magnesium sulfate. The organic layer was evaporated and the resulting solid was recrystallized from ethyl acetate. 11.8 g of compound (A) was obtained as a yellow solid. (LC purity 96%, yield 59%)

Compound (A) (10.0 g, 25 mmol), NH ₂ OH · HCl (4.33 g, 63.3 mmol), and sodium acetate (5.70 g, 69.5 mmol) were mixed in 150 ml of isopropanol and mixed at 80 ° C. for 4 hours. Reacted for hours.
After completion of the reaction, the solvent was distilled off under reduced pressure, 150 ml of ethyl acetate was added, and the mixture was stirred with heating. After cooling, suction filtration was performed to remove NaCl. The filtrate was washed twice with 30 ml of saturated brine and dried over magnesium sulfate. The solvent was evaporated, 50 ml of a mixed solvent of ethyl acetate / hexane = 1/1 was added to the residue, heated and stirred for 5 to 10 minutes, the supernatant was removed by decantation, and the residue was vacuum dried.
The obtained solid was recrystallized from dichloromethane to obtain 10.5 g of Compound (B) (LC purity 97%, yield 90%).

Compound (B) (9.33 g, 20 mmol) and acetyl chloride (7.85 g, 100 mmol) were dissolved in 100 g of dichloromethane and cooled on ice.
Triethylamine (10.11 g, 100 mmol) was added dropwise over 1 hour. After completion of the dropping, the reaction was performed at room temperature for 4 hours. Next, 100 mL of water and 30 g of dichloromethane were added to separate the organic layer, and then washed twice with a saturated NH ₄ Cl aqueous solution _three times with a 5 wt% Na ₂ CO ₃ aqueous solution and then twice with a saturated saline solution. , Dried over sodium sulfate and evaporated. The residue was purified by a column using a mixed solvent of ethyl acetate / hexane = 2/1 to obtain 10.8 g of compound (X1) (LC purity 96%, yield 94%).

<Absorption evaluation results and evaluation conditions of 340 nm to 700 nm>
The obtained compound (X1) was tested for absorption at 340 to 700 nm by the following method. As a result, λmax was 383 nm and ε was 7880.
(Measurement of absorption maximum)
The absorption maximum of the compound (X1) was measured by dissolving the compound (X1) in tetrahydrofuran so as to have a concentration of 10 ^−5, and using an ultraviolet and visible light spectrometer.

<Toluene solubility evaluation results and evaluation conditions:>
The obtained compound (X1) was tested for solubility in a solvent by the following method. As a result, it was confirmed that the compound (X1) was completely dissolved at both a concentration of 1.0% by weight and a concentration of 2.0% by weight. It was.
(Solubility test)
With respect to 100 g of toluene, the concentration of the compound (X1) was 1% by weight and 2% by weight, respectively, and dissolved at normal pressure of 25 ° C., and the presence or absence of undissolved component residues was visually observed.

<Creation of hologram recording medium>
In sample bottle 1, compound of 8.418 g of 2-methylhexanol (2EH) added to multimer of hexamethylene diisocyanate (HMDI), 1.778 g of tribromophenyl acrylate, photopolymerization initiator of the above compound (X1) 0. 089 g was weighed and stirred until each component was dissolved.
Next, 7.582 g of polycaprolactone triol having a molecular weight of 500 and 0.0032 g of dioctyltin dilaurate were weighed in the sample bottle 2 and stirred until each component was dissolved.
Thereafter, the sample bottles 1 and 2 were put in a bell jar and degassed in vacuum for 3 hours, and then the liquids in the sample bottles 1 and 2 were mixed and stirred and mixed, and degassed in vacuum by the bell jar for several minutes.
Subsequently, a vacuum degassed solution was poured onto a glass slide with a 500 μm thick Teflon sheet as a spacer on the two ends, and the glass slide was placed on it, and the periphery was fixed with a clip at 60 ° C. Was heated for 15 hours to prepare a recording layer.

<Diffraction efficiency evaluation results and evaluation conditions after 5 minutes of recording>
When hologram recording was performed using the above-described sample of the hologram recording medium according to the procedure described below, the diffraction efficiency was 8%.

(Evaluation conditions for hologram recording)
An outline of the apparatus used for hologram recording is shown in FIG.
In FIG. 1, S represents a sample of a hologram recording medium, M1 to M3 all represent mirrors, PBS represents a polarizing beam splitter, L1 represents a laser light source for recording light that emits light having a wavelength of 405 nm, and L2 represents A laser light source for reproducing light that emits light having a wavelength of 633 nm is shown, and PD1 and PD2 are photodetectors.
As a light source for hologram recording, a light source capable of obtaining a blue laser beam having a wavelength of 405 nm (single mode laser diode manufactured by Sony Corporation: “L1” in the figure) was used. The light having a wavelength of 405 nm was divided by a polarizing beam splitter (“PBS” in the figure) and crossed on the recording surface so that the angle formed by the two beams was 50.00 degrees. At this time, the bisector of the angle formed by the two beams is perpendicular to the recording surface, and the vibration planes of the electric field vectors of the two beams obtained by the division are two intersecting lines. Irradiation was performed so as to be perpendicular to the plane including the beam.
After hologram recording, using a He-Ne laser that can obtain light having a wavelength of 633 nm (V05-LHP151 manufactured by Meles Griot: “L2” in the figure), the light is irradiated at an angle of 30.19 degrees with respect to the recording surface. If the diffracted light is detected by using a power meter and a detector (Newport 2930-C, 918-SL: “PD1” and “PD2” in the figure), whether hologram recording is performed correctly. Judged whether or not. The diffraction efficiency of a hologram is given by the ratio of the intensity of diffracted light to the intensity of incident light.

[Example 2]
<Production of hologram recording medium>
In the sample bottle 1, 3.162 g of hexamethylene diisocyanate, 1.111 g of tribromophenyl acrylate and 0.056 g of the photopolymerization initiator of the compound (X1) synthesized in Example 1 were weighed and stirred until each component was dissolved.
Next, 6.838 g of polycaprolactone triol having a molecular weight of 500 and 0.0020 g of dioctyltin dilaurate were weighed in the sample bottle 2 and stirred until each component was dissolved.
Thereafter, the sample bottles 1 and 2 were put in a bell jar and degassed in vacuum for 3 hours, and then the liquids in the sample bottles 1 and 2 were mixed and stirred and mixed, and degassed in vacuum by the bell jar for several minutes.

  Subsequently, a vacuum degassed solution was poured onto a glass slide with a 500 μm thick Teflon sheet as a spacer on the two ends, and the glass slide was placed on it, and the periphery was fixed with a clip at 60 ° C. Was heated for 15 hours to prepare a recording layer.

<Diffraction efficiency evaluation results after 5 minutes of recording>
When hologram recording was performed in the same procedure as in Example 1, the diffraction efficiency was 10%.

[Example 3]
<Production of hologram recording medium>
Light of compound (X1) synthesized in Example 1, 5.250 g of compound in which 2-ethylhexanol is added to hexamethylene diisocyanate multimer in sample bottle 1, 1.111 g of paracumylphenol EO-modified (n≈1) acrylate 0.056 g of a polymerization initiator was weighed and stirred until each component was dissolved.
Next, 4.750 g of polycaprolactone triol having a molecular weight of 500 and 0.003 g of dioctyltin dilaurate were weighed in the sample bottle 2 and stirred until each component was dissolved.
Thereafter, the sample bottles 1 and 2 were put in a bell jar and degassed in vacuum for 3 hours, and then the liquids in the sample bottles 1 and 2 were mixed and stirred and mixed, and degassed in vacuum by the bell jar for several minutes.
Subsequently, a vacuum degassed solution was poured onto a glass slide with a 500 μm thick Teflon sheet as a spacer on the two ends, and the glass slide was placed on it, and the periphery was fixed with a clip at 60 ° C. Was heated for 15 hours to prepare a recording layer.

<Diffraction efficiency evaluation results after 5 minutes of recording>
When hologram recording was performed in the same procedure as in Example 1, the diffraction efficiency was 14%.

[Example 4]
<Production of hologram recording medium>
8.418 g of a compound obtained by adding 2-ethylhexanol to a multimer of hexamethylene diisocyanate in sample bottle 1, 1.778 g of tribromophenyl acrylate, 0.089 g of a photopolymerization initiator of compound (X1) synthesized in Example 1, 0.0018 g of terpinolene was weighed and stirred until each component was dissolved.
Next, 7.582 g of polycaprolactone triol having a molecular weight of 500 and 0.0032 g of dioctyltin dilaurate were weighed in the sample bottle 2 and stirred until each component was dissolved.
Thereafter, the sample bottles 1 and 2 were put in a bell jar and degassed in vacuum for 3 hours, and then the liquids in the sample bottles 1 and 2 were mixed and stirred and mixed, and degassed in vacuum by the bell jar for several minutes.
Subsequently, a vacuum degassed solution was poured onto a glass slide with a 500 μm thick Teflon sheet as a spacer on the two ends, and the glass slide was placed on it, and the periphery was fixed with a clip at 60 ° C. Was heated for 15 hours to prepare a recording layer.

<Diffraction efficiency evaluation results after 5 minutes of recording>
When hologram recording was performed in the same procedure as in Example 1, the diffraction efficiency was 8%.

[Comparative Example 1]
Instead of the compound (X1) synthesized in Example 1, the following compound (Z1) was used as a photopolymerization initiator.

<Absorption evaluation results and evaluation conditions of 340 nm to 700 nm>
The compound (Z1) was tested for absorption at 340 to 700 nm in the same manner as in Example 1. As a result, λmax = 336 nm and ε = 20300.

<Toluene solubility evaluation results and evaluation conditions>
Compound (Z1) was tested for solubility in a solvent in the same manner as in Example 1. As a result, it was confirmed that the compound (Z1) was completely dissolved at both a concentration of 1.0% by weight and a concentration of 2.0% by weight. It was done.

<Production of hologram recording medium>
A hologram recording medium was produced in the same manner as in Example 1 except that the compound (Z1) was used in place of the compound (X1) as a photopolymerization initiator.

<Diffraction efficiency evaluation results after 5 minutes of recording>
Hologram recording was performed in the same procedure as in Example 1, but almost no signal was generated.

[Comparative Example 2]
In place of the compound (X1) synthesized in Example 1, the following compound (Z2) was used as a photopolymerization initiator to try to form a recording layer in the same manner, but the recording layer was not dissolved in other components. Could not be formed.

<Absorption evaluation results and evaluation conditions of 340 nm to 700 nm>
The compound (Z2) was tested for absorption at 340 to 700 nm in the same manner as in Example 1. As a result, λmax = 383 nm and ε = 6275.

<Toluene solubility evaluation results and evaluation conditions>
Compound (Z2) was tested for solubility in a solvent by the same method as in Example 1. As a result, it was not dissolved at a concentration of 1.0% by weight.

  The above evaluation results are summarized in Table 1.

  As shown in Table 1, the hologram optical recording media of Examples 1 to 4 have high diffraction efficiency and good hologram recording, whereas Comparative Example 1 has almost no signal. In Comparative Example 2, the hologram recording medium could not be produced because the photopolymerization initiator was not dissolved in other components.

  The composition for forming a hologram recording layer of the present invention and the hologram recording material using the composition are suitably used for applications such as a hologram optical recording medium.

It is a figure for demonstrating the outline | summary of the apparatus used for the hologram recording in an Example.

Explanation of symbols

S Sample M1 to M3 Mirror PBS Polarizing beam splitter L1 Laser light source for recording light L2 Laser light source for reproduction light PD1, PD2 Photo detector

Claims (8)

A composition for forming a holographic recording layer capable of forming a photoimage containing a polymerizable photoactive compound (a) used for a holographic optical recording medium, wherein the composition has a structure represented by the following general formula (I): And a composition for forming a hologram recording layer, comprising a photopolymerization initiator (b) having an absorption maximum in a wavelength range of 340 to 700 nm and a solubility in toluene of 1 (g / 100 g) or more. .

[In the formula, each R ² optionally has a substituent, an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a benzoyl group, An alkoxycarbonyl group having 2 to 10 carbon atoms, a phenoxycarbonyl group, a heteroaryl group having 1 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, or an aminocarbonyl group having 1 to 20 carbon atoms is shown.
X and Y each independently represent an arbitrary substituent. ] The composition for forming a hologram recording layer according to claim 1, wherein the photopolymerization initiator (b) is a compound represented by the following general formula (II).

(In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aminoalkyl group having 1 to 12 carbon atoms which may have a substituent, or a substituent. Or an alkenyl group having 2 to 20 carbon atoms, or a group represented by the following general formula (IIa).

[Wherein, R ^{2 ″} , R ^{3 ′} , R ^{4 ′} , R ^{5 ′} , R ^{6 ′,} and R ^{7 ′} each independently represent R ² in general formula (II) independently of that in general formula (II). ^′ , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^7, and * in the formula means bonding to a carbon atom in the general formula (II) at the portion *.
R ^{2 ′} each may have a substituent, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 4 to 6 carbon atoms, a benzoyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a phenoxycarbonyl group. Indicates.
R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, carbon, which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 Represents an alkoxycarbonyl group, a phenoxycarbonyl group, or —OR ⁸ , —SR ⁹ , —SOR ⁹ , —SO ₂ R ⁹ or —NR ¹⁰ R ¹¹ , and R ³ , R ⁴ , R ⁵ , R ^6. And at least one of R ⁷ represents —OR ⁸ , —SR ⁹ , or —NR ¹⁰ R ¹¹ .
However, R ⁸ is a hydrogen atom, or, respectively may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 8 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, carbon An alkenoyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a phenyl group, — (CH ₂ CH ₂ O) _n H (n is an integer of 1 to 20), or alkylsilyl having 3 to 20 carbon atoms Indicates a group.
R ⁹ is a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or phenyl. Indicates a group.
R ¹⁰ and R ¹¹ are each independently a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, or 3 to 3 carbon atoms, each optionally having a substituent. An alkenoyl group having 6 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a phenyl group, a benzoyl group, or a biphenyl group; The phenyl group, benzoyl group, and biphenyl group may be bonded via an optionally substituted alkylene group having 2 to 8 carbon atoms.
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may be bonded to each other to form a ring structure. ] The composition for forming a hologram recording layer according to claim 2, wherein the photopolymerization initiator (b) is a compound represented by the following general formula (III).

Wherein, R ¹ and R ^{2 'are} R ¹ and R ² in the general formula ^(II)' is synonymous with.
R ^{3 ″} , R ^{6 ″} and R ^{7 ″} each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 3 to 3 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 12 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A group or a phenoxycarbonyl group;
R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, each having a substituent, and 2 to 2 carbon atoms. 12 alkenoyl groups, alkoxy groups having 1 to 12 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, phenyl groups, benzyl groups, benzoyl groups, alkanoyl groups having 2 to 20 carbon atoms, alkoxycarbonyl having 2 to 12 carbon atoms A group, a phenoxycarbonyl group, an amide group or a nitro group; ] The composition for forming a hologram recording layer according to claim 2, wherein the photopolymerization initiator (b) is a compound represented by the following general formula (IV).

[Wherein, R ¹ and R ^{2 ′} have the same meanings as R ¹ and R ^{2 ′ in} formula (II), respectively.
R ^{3 ″ ′} , R ^{6 ″ ′} and R ^{7 ″ ′} are independently of each other a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent. C3-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C12 alkanoyl group, C2-C12 An alkoxycarbonyl group or a phenoxycarbonyl group.
R ^{12 ′} , R ^{13 ′} , R ^{14 ′} and R ^{15 ′} are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms which may have a substituent, C2-C12 alkenoyl group, C1-C12 alkoxy group, C5-C8 cycloalkyl group, phenyl group, benzyl group, benzoyl group, C2-C20 alkanoyl group, C2-C2 12 alkoxycarbonyl groups, phenoxycarbonyl groups, amide groups or nitro groups are shown.
R ¹⁶ is a hydroxyl group, a thiol group, a nitro group, a cyano group, or a cycloalkenyl group having 3 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, or a carbon number, each optionally having a substituent. 6-18 aryl group, C2-C18 alkenyloxy group, C2-C18 alkenylthio group, acyl group, carboxyl group, acyloxy group, amino group, acylamino group, carbamate group, carbamoyl group, carboxylic acid An ester group, a sulfamoyl group, a sulfonic acid ester group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a pyrrolidinyl group, a tetrahydrothiophene dioxide group, or a trialkylsilyl group. ]   The composition for forming a hologram recording layer according to any one of claims 1 to 4, further comprising a resin matrix (c).   The composition for forming a hologram recording layer according to any one of claims 1 to 5, wherein the photoactive compound (a) is a radical polymerizable monomer.   A hologram recording material comprising the composition for forming a hologram recording layer according to any one of claims 1 to 6.   A hologram optical recording medium comprising a layer containing the hologram recording material according to claim 7.

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